{"product_id":"stable-radicals-fundamentals-and-applied-aspects-of-odd-electron-compounds-hardback-9780470770832","title":"Stable Radicals; Fundamentals and Applied Aspects of Odd-Electron Compounds (Hardback) 9780470770832","description":"\u003cfont face=\"Georgia\"\u003e\r\n\u003cp\u003e\u003cfont size=\"6\"\u003eStable Radicals\u003c\/font\u003e\u003cbr\u003e\r\n\u003cfont size=\"5\"\u003eFundamentals and Applied Aspects of Odd-Electron Compounds\u003c\/font\u003e\u003c\/p\u003e\r\n\r\n\r\n\r\n\r\n\u003cp\u003e\u003cfont size=\"4\"\u003eRobin Hicks (Edited by), R Hicks (Author)\u003c\/font\u003e\u003c\/p\u003e\r\n\r\n\u003cp\u003e\u003cfont size=\"3\"\u003e9780470770832, Wiley\u003c\/font\u003e\u003c\/p\u003e\r\n\r\n\u003cp\u003e\u003cfont size=\"3\"\u003eHardback, published 9 July 2010\u003c\/font\u003e\u003c\/p\u003e\r\n\r\n\u003cp\u003e\u003cfont size=\"3\"\u003e624 pages\u003cbr\u003e25.2 x 19.6 x 3.6 cm, 1.361 kg\u003c\/font\u003e\u003c\/p\u003e\r\n\r\n\r\n\r\n\u003cp align=\"justify\"\u003e\u003cem\u003e\u003cfont size=\"3\"\u003e\u003cp\u003e\"This is a worthwhile and insightful anthology and leaves the reader with the impression that novel prospects and discoveries could surface at any moment from junctions on the stable radical chemical topology.\" (\u003ci\u003eAngewandte Chemie\u003c\/i\u003e, 2011)\u003c\/p\u003e\u003c\/font\u003e\u003c\/em\u003e\u003c\/p\u003e\r\n\r\n\u003cp align=\"justify\"\u003e\u003cstrong\u003e\u003cfont size=\"3\"\u003e\u003cp\u003eStable radicals - molecules with odd electrons which are sufficiently long lived to be studied or isolated using conventional techniques - have enjoyed a long history and are of current interest for a broad array of fundamental and applied reasons, for example to study and drive novel chemical reactions, in the development of rechargeable batteries or the study of free radical reactions in the body.\u003c\/p\u003e \u003cp\u003eIn \u003ci\u003eStable Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds\u003c\/i\u003e a team of international experts provide a broad-based overview of stable radicals, from the fundamental aspects of specific classes of stable neutral radicals to their wide range of applications including synthesis, materials science and chemical biology. Topics covered include:\u003c\/p\u003e \u003cul\u003e \u003cli\u003etriphenylmethyl and related radicals\u003c\/li\u003e \u003cli\u003epolychlorinated triphenylmethyl radicals: towards multifunctional molecular materials\u003c\/li\u003e \u003cli\u003ephenalenyls, cyclopentadienyls, and other carbon-centered radicals\u003c\/li\u003e \u003cli\u003ethe nitrogen oxides: persistent radicals and van der Waals complex dimers\u003c\/li\u003e \u003cli\u003enitroxide radicals: properties, synthesis and applications\u003c\/li\u003e \u003cli\u003ethe only stable organic sigma radicals: di-tert-alkyliminoxyls.\u003c\/li\u003e \u003cli\u003edelocalized radicals containing the hydrazyl [R2N-NR] unit\u003c\/li\u003e \u003cli\u003emetal-coordinated phenoxyl radicals\u003c\/li\u003e \u003cli\u003estable radicals containing the thiazyl unit: synthesis, chemical, and materials properties\u003c\/li\u003e \u003cli\u003estable radicals of the heavy p-block elements\u003c\/li\u003e \u003cli\u003eapplication of stable radicals as mediators in living-radical polymerization\u003c\/li\u003e \u003cli\u003enitroxide-catalyzed alcohol oxidations in organic synthesis\u003c\/li\u003e \u003cli\u003emetal-nitroxide complexes: synthesis and magneto-structural correlations\u003c\/li\u003e \u003cli\u003erechargeable batteries using robust but redox-active organic radicals\u003c\/li\u003e \u003cli\u003espin labeling: a modern perspective\u003c\/li\u003e \u003cli\u003efunctional in vivo EPR spectroscopy and imaging using nitroxides and trityl radicals\u003c\/li\u003e \u003cli\u003ebiologically relevant chemistry of nitroxides\u003c\/li\u003e \u003c\/ul\u003e \u003cp\u003e\u003ci\u003eStable Free Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds\u003c\/i\u003e is an essential guide to this fascinating area of chemistry for researchers and students working in organic and physical chemistry and materials science.\u003c\/p\u003e\u003c\/font\u003e\u003c\/strong\u003e\u003c\/p\u003e\r\n\r\n\u003cp\u003e\u003cfont size=\"3\"\u003e\u003cp\u003ePreface xv\u003cbr\u003e\u003cbr\u003eList of Contributors xvii\u003c\/p\u003e \u003cp\u003e\u003cb\u003e1. Triarylmethyl and Related Radicals 1\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eThomas T. Tidwell\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e1.1 Introduction 1\u003c\/p\u003e \u003cp\u003e1.1.1 Discovery of the triphenylmethyl radical 1\u003c\/p\u003e \u003cp\u003e1.1.2 Bis(triphenylmethyl) peroxide 3\u003c\/p\u003e \u003cp\u003e1.2 Free radical rearrangements 4\u003c\/p\u003e \u003cp\u003e1.3 Other routes to triphenylmethyl radicals 5\u003c\/p\u003e \u003cp\u003e1.4 The persistent radical effect 7\u003c\/p\u003e \u003cp\u003e1.5 Properties of triphenylmethyl radicals 8\u003c\/p\u003e \u003cp\u003e1.6 Steric effects and persistent radicals 9\u003c\/p\u003e \u003cp\u003e1.7 Substituted triphenylmethyl radicals and dimers 9\u003c\/p\u003e \u003cp\u003e1.8 Tris(heteroaryl)methyl and related triarylmethyl radicals 12\u003c\/p\u003e \u003cp\u003e1.9 Delocalized persistent radicals: analogues of triarylmethyl radicals 14\u003c\/p\u003e \u003cp\u003e1.10 Tetrathiatriarylmethyl (TAM) and related triarylmethyl radicals 16\u003c\/p\u003e \u003cp\u003e1.11 Perchlorinated triarylmethyl radicals 20\u003c\/p\u003e \u003cp\u003e1.12 Other triarylmethyl radicals 23\u003c\/p\u003e \u003cp\u003e1.13 Diradicals and polyradicals related to triphenylmethyl 24\u003c\/p\u003e \u003cp\u003e1.14 Outlook 28\u003c\/p\u003e \u003cp\u003eAcknowledgements 28\u003c\/p\u003e \u003cp\u003eReferences 28\u003c\/p\u003e \u003cp\u003e\u003cb\u003e2. Polychlorotriphenylmethyl Radicals: Towards Multifunctional Molecular Materials 33\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eJaume Veciana and Imma Ratera\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e2.1 Introduction 33\u003c\/p\u003e \u003cp\u003e2.2 Functional molecular materials based on PTM radicals 35\u003c\/p\u003e \u003cp\u003e2.2.1 Materials with magnetic properties 37\u003c\/p\u003e \u003cp\u003e2.2.2 Materials with electronic properties 53\u003c\/p\u003e \u003cp\u003e2.2.3 Materials with optical properties 65\u003c\/p\u003e \u003cp\u003e2.3 Multifunctional switchable molecular materials based on PTM radicals 69\u003c\/p\u003e \u003cp\u003e2.3.1 Photo switchable molecular systems 69\u003c\/p\u003e \u003cp\u003e2.3.2 Redox switchable molecular systems 70\u003c\/p\u003e \u003cp\u003e2.4 Conclusions 75\u003c\/p\u003e \u003cp\u003eReferences 76\u003c\/p\u003e \u003cp\u003e\u003cb\u003e3. Phenalenyls, Cyclopentadienyls, and Other Carbon-Centered Radicals 81\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eYasushi Morita and Shinsuke Nishida\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e3.1 Introduction 81\u003c\/p\u003e \u003cp\u003e3.2 Open shell graphene 82\u003c\/p\u003e \u003cp\u003e3.3 Phenalenyl 84\u003c\/p\u003e \u003cp\u003e3.4 2,5,8-Tri-tert-butylphenalenyl radical 86\u003c\/p\u003e \u003cp\u003e3.5 Perchlorophenalenyl radical 92\u003c\/p\u003e \u003cp\u003e3.6 Dithiophenalenyl radicals 94\u003c\/p\u003e \u003cp\u003e3.7 Nitrogen-containing phenalenyl systems 97\u003c\/p\u003e \u003cp\u003e3.7.1 Molecular design and topological isomers 97\u003c\/p\u003e \u003cp\u003e3.7.2 2,5,8-Tri-tert-butyl-1,3-diazaphenalenyl 97\u003c\/p\u003e \u003cp\u003e3.7.3 Hexaazaphenalenyl derivatives 102\u003c\/p\u003e \u003cp\u003e3.7.4 β-Azaphenalenyl derivatives 103\u003c\/p\u003e \u003cp\u003e3.8 Oxophenalenoxyl systems 106\u003c\/p\u003e \u003cp\u003e3.8.1 Molecular design and topological isomers 106\u003c\/p\u003e \u003cp\u003e3.8.2 3-Oxophenalenoxyl (3OPO) system 108\u003c\/p\u003e \u003cp\u003e3.8.3 4- and 6-Oxophenalenoxyl (4OPO, 6OPO) systems 110\u003c\/p\u003e \u003cp\u003e3.8.4 Redox-based spin diversity 114\u003c\/p\u003e \u003cp\u003e3.8.5 Molecular crystalline secondary battery 115\u003c\/p\u003e \u003cp\u003e3.8.6 Spin-center transfer and solvato-\/thermochromism 117\u003c\/p\u003e \u003cp\u003e3.9 Phenalenyl-based zwitterionic radicals 119\u003c\/p\u003e \u003cp\u003e3.10 π-Extended phenalenyl systems 122\u003c\/p\u003e \u003cp\u003e3.10.1 Triangulenes 122\u003c\/p\u003e \u003cp\u003e3.10.2 Trioxytriangulene with redox-based spin diversity nature 125\u003c\/p\u003e \u003cp\u003e3.10.3 Bis- and tris-phenalenyl system and singlet biradical characters 125\u003c\/p\u003e \u003cp\u003e3.11 Curve-structured phenalenyl system 130\u003c\/p\u003e \u003cp\u003e3.12 Non-alternant stable radicals 131\u003c\/p\u003e \u003cp\u003e3.12.1 Cyclopentadienyl radicals 131\u003c\/p\u003e \u003cp\u003e3.12.2 Cyclopentadienyl radicals within a larger π-electronic framework 135\u003c\/p\u003e \u003cp\u003e3.13 Stable triplet carbenes 136\u003c\/p\u003e \u003cp\u003e3.14 Conclusions 139\u003c\/p\u003e \u003cp\u003eAcknowledgements 139\u003c\/p\u003e \u003cp\u003eReferences 140\u003c\/p\u003e \u003cp\u003e\u003cb\u003e4. The Nitrogen Oxides: Persistent Radicals and van der Waals Complex Dimers 147\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eD. Scott Bohle\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e4.1 Introduction 147\u003c\/p\u003e \u003cp\u003e4.2 Synthetic access 149\u003c\/p\u003e \u003cp\u003e4.3 Physical properties 149\u003c\/p\u003e \u003cp\u003e4.4 Structural chemistry of the monomers and dimers 150\u003c\/p\u003e \u003cp\u003e4.4.1 Nitric oxide and dinitrogen dioxide 150\u003c\/p\u003e \u003cp\u003e4.4.2 Nitrogen dioxide and dinitrogen tetroxide 152\u003c\/p\u003e \u003cp\u003e4.5 Electronic structure of nitrogen oxides 153\u003c\/p\u003e \u003cp\u003e4.6 Reactivity of nitric oxide and nitrogen dioxide and their van der Waals complexes 155\u003c\/p\u003e \u003cp\u003e4.7 The kinetics of nitric oxide’s termolecular reactions 156\u003c\/p\u003e \u003cp\u003e4.8 Biochemical and organic reactions of nitric oxide 158\u003c\/p\u003e \u003cp\u003e4.9 General reactivity patterns 160\u003c\/p\u003e \u003cp\u003e4.9.1 Oxidation 160\u003c\/p\u003e \u003cp\u003e4.9.2 Reduction 161\u003c\/p\u003e \u003cp\u003e4.9.3 Coordination 162\u003c\/p\u003e \u003cp\u003e4.9.4 Addition of nucleophiles 162\u003c\/p\u003e \u003cp\u003e4.9.5 General organic reactions 165\u003c\/p\u003e \u003cp\u003e4.9.6 Reactions with other nucleophiles 165\u003c\/p\u003e \u003cp\u003e4.10 The colored species problem in nitric oxide chemistry 166\u003c\/p\u003e \u003cp\u003e4.11 Conclusions 166\u003c\/p\u003e \u003cp\u003eReferences 166\u003c\/p\u003e \u003cp\u003e\u003cb\u003e5. Nitroxide Radicals: Properties, Synthesis and Applications 173\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eHakim Karoui, François Le Moigne, Olivier Ouari and Paul Tordo\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e5.1 Introduction 173\u003c\/p\u003e \u003cp\u003e5.2 Nitroxide structure 174\u003c\/p\u003e \u003cp\u003e5.2.1 Characteristics of the aminoxyl group 174\u003c\/p\u003e \u003cp\u003e5.2.2 X-ray structures of nitroxides 175\u003c\/p\u003e \u003cp\u003e5.2.3 Quantum mechanical (QM), molecular dynamics (MD) and molecular mechanics (MM) calculations 177\u003c\/p\u003e \u003cp\u003e5.2.4 Influence of solvent polarity on the EPR parameters of nitroxides 180\u003c\/p\u003e \u003cp\u003e5.3 Nitroxide multiradicals 181\u003c\/p\u003e \u003cp\u003e5.3.1 Electron spin–spin exchange coupling 182\u003c\/p\u003e \u003cp\u003e5.3.2 Miscellaneous aspects of di- and polynitroxides 184\u003c\/p\u003e \u003cp\u003e5.4 Nitronyl nitroxides (NNOs) 185\u003c\/p\u003e \u003cp\u003e5.4.1 Synthesis of nitronyl nitroxides 186\u003c\/p\u003e \u003cp\u003e5.4.2 Nitronyl nitroxide as a nitric oxide trap 186\u003c\/p\u003e \u003cp\u003e5.4.3 Nitronyl nitroxides as building blocks for magnetic materials 188\u003c\/p\u003e \u003cp\u003e5.5 Synthesis of nitroxides 191\u003c\/p\u003e \u003cp\u003e5.5.1 Oxidation of amines 191\u003c\/p\u003e \u003cp\u003e5.5.2 Oxidation of hydroxylamines 191\u003c\/p\u003e \u003cp\u003e5.5.3 Chiral nitroxides 191\u003c\/p\u003e \u003cp\u003e5.5.4 Nitroxide design for nitroxide mediated polymerization (NMP) 193\u003c\/p\u003e \u003cp\u003e5.6 Chemical properties of nitroxides 196\u003c\/p\u003e \u003cp\u003e5.6.1 The Persistent Radical Effect 197\u003c\/p\u003e \u003cp\u003e5.6.2 Redox reactions 197\u003c\/p\u003e \u003cp\u003e5.6.3 Approaches to improve the resistance of nitroxides toward bioreduction 198\u003c\/p\u003e \u003cp\u003e5.6.4 Hydrogen abstraction reactions 199\u003c\/p\u003e \u003cp\u003e5.6.5 Cross-coupling reactions 200\u003c\/p\u003e \u003cp\u003e5.6.6 Nitroxides in synthetic sequences 200\u003c\/p\u003e \u003cp\u003e5.7 Nitroxides in supramolecular entities 206\u003c\/p\u003e \u003cp\u003e5.7.1 Interaction of nitroxides with cyclodextrins 207\u003c\/p\u003e \u003cp\u003e5.7.2 Interaction of nitroxides with calix[4]arenes 209\u003c\/p\u003e \u003cp\u003e5.7.3 Interaction of nitroxides with curcubiturils 210\u003c\/p\u003e \u003cp\u003e5.7.4 Interaction of nitroxides with micelles 211\u003c\/p\u003e \u003cp\u003e5.7.5 Fullerene-linked nitroxides 212\u003c\/p\u003e \u003cp\u003e5.8 Nitroxides for dynamic nuclear polarization (DNP) enhanced NMR 213\u003c\/p\u003e \u003cp\u003e5.8.1 DNP for biological NMR and real-time metabolic imaging 213\u003c\/p\u003e \u003cp\u003e5.8.2 Nitroxides as polarizing agents for DNP 214\u003c\/p\u003e \u003cp\u003e5.9 Nitroxides as pH-sensitive spin probes 216\u003c\/p\u003e \u003cp\u003e5.10 Nitroxides as prefluorescent probes 217\u003c\/p\u003e \u003cp\u003e5.11 EPR-spin trapping technique 217\u003c\/p\u003e \u003cp\u003e5.11.1 Immuno spin trapping 219\u003c\/p\u003e \u003cp\u003e5.11.2 Conclusion 219\u003c\/p\u003e \u003cp\u003e5.12 Conclusions 220\u003c\/p\u003e \u003cp\u003eReferences 220\u003c\/p\u003e \u003cp\u003e\u003cb\u003e6. The Only Stable Organic Sigma Radicals: Di-tert-Alkyliminoxyls 231\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eKeith U. Ingold\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e6.1 Introduction 231\u003c\/p\u003e \u003cp\u003e6.2 The discovery of stable iminoxyls 232\u003c\/p\u003e \u003cp\u003e6.2.1 Synthesis of di-tert-butyl ketoxime 233\u003c\/p\u003e \u003cp\u003e6.2.2 Synthesis of di-tert-butyliminoxyl 234\u003c\/p\u003e \u003cp\u003e6.2.3 Stability of di-tert-butyliminoxyl 235\u003c\/p\u003e \u003cp\u003e6.3 Hydrogen atom abstraction by di-tert-butyliminoxyl 236\u003c\/p\u003e \u003cp\u003e6.3.1 The O−H bond dissociation enthalpy (BDE) in (Me 3 C) 2 C=NOH 236\u003c\/p\u003e \u003cp\u003e6.3.2 Oxidation of hydrocarbons with di-tert-butyliminoxyl 237\u003c\/p\u003e \u003cp\u003e6.3.3 Oxidation of phenols with di-tert-butyliminoxyl 238\u003c\/p\u003e \u003cp\u003e6.3.4 Oxidation of amines with di-tert-butyliminoxyl 239\u003c\/p\u003e \u003cp\u003e6.3.5 Oxidation of di-tert-butylketoxime with di-tert-butyliminoxyl 239\u003c\/p\u003e \u003cp\u003e6.4 Other reactions and non-reactions of di-tert-butyliminoxyl 241\u003c\/p\u003e \u003cp\u003e6.5 Di-tert-alkyliminoxyls more sterically crowded than di-tert-butyliminoxyl 241\u003c\/p\u003e \u003cp\u003e6.6 Di-(1-Adamantyl)iminoxyl: a truly stable σ radical 242\u003c\/p\u003e \u003cp\u003eReferences 243\u003c\/p\u003e \u003cp\u003e\u003cb\u003e7. Verdazyls and Related Radicals Containing the Hydrazyl [R 2 N−NR] Group 245\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eRobin G. Hicks\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e7.1 Introduction 245\u003c\/p\u003e \u003cp\u003e7.2 Verdazyl radicals 246\u003c\/p\u003e \u003cp\u003e7.2.1 Synthesis of verdazyls 246\u003c\/p\u003e \u003cp\u003e7.2.2 Stability, physical properties and electronic structure of verdazyls 250\u003c\/p\u003e \u003cp\u003e7.2.3 Verdazyl radical reactivity 256\u003c\/p\u003e \u003cp\u003e7.2.4 Inorganic verdazyl analogues 264\u003c\/p\u003e \u003cp\u003e7.3 Tetraazapentenyl radicals 265\u003c\/p\u003e \u003cp\u003e7.4 Tetrazolinyl radicals 266\u003c\/p\u003e \u003cp\u003e7.5 1,2,4-Triazolinyl radicals 268\u003c\/p\u003e \u003cp\u003e7.6 1,2,4,5-Tetrazinyl radicals 269\u003c\/p\u003e \u003cp\u003e7.7 Benzo-1,2,4-triazinyl radicals 270\u003c\/p\u003e \u003cp\u003e7.8 Summary 273\u003c\/p\u003e \u003cp\u003eReferences 273\u003c\/p\u003e \u003cp\u003e\u003cb\u003e8. Metal Coordinated Phenoxyl Radicals 281\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eFabrice Thomas\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e8.1 Introduction 281\u003c\/p\u003e \u003cp\u003e8.2 General properties of phenoxyl radicals 282\u003c\/p\u003e \u003cp\u003e8.2.1 Electronic structure and stabilization 282\u003c\/p\u003e \u003cp\u003e8.2.2 Electrochemistry of phenoxyl radicals 283\u003c\/p\u003e \u003cp\u003e8.2.3 Structure of non-coordinated phenoxyl radicals 284\u003c\/p\u003e \u003cp\u003e8.2.4 UV-Vis spectroscopy 284\u003c\/p\u003e \u003cp\u003e8.2.5 EPR spectroscopy 284\u003c\/p\u003e \u003cp\u003e8.3 Occurrence of tyrosyl radicals in proteins 285\u003c\/p\u003e \u003cp\u003e8.4 Complexes with coordinated phenoxyl radicals 287\u003c\/p\u003e \u003cp\u003e8.4.1 General ligand structures 287\u003c\/p\u003e \u003cp\u003e8.4.2 Vanadium complexes 290\u003c\/p\u003e \u003cp\u003e8.4.3 Chromium complexes 291\u003c\/p\u003e \u003cp\u003e8.4.4 Manganese complexes 292\u003c\/p\u003e \u003cp\u003e8.4.5 Iron complexes 294\u003c\/p\u003e \u003cp\u003e8.4.6 Cobalt complexes 297\u003c\/p\u003e \u003cp\u003e8.4.7 Nickel complexes 299\u003c\/p\u003e \u003cp\u003e8.4.8 Copper complexes 303\u003c\/p\u003e \u003cp\u003e8.4.9 Zinc complexes 310\u003c\/p\u003e \u003cp\u003e8.5 Conclusions 313\u003c\/p\u003e \u003cp\u003e8.6 Abbreviations 313\u003c\/p\u003e \u003cp\u003eReferences 313\u003c\/p\u003e \u003cp\u003e\u003cb\u003e9. The Synthesis and Characterization of Stable Radicals Containing the Thiazyl (SN) Fragment and Their Use as Building Blocks for Advanced Functional Materials\u003c\/b\u003e 317\u003cbr\u003e\u003ci\u003eRobin G. Hicks\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e9.1 Introduction 317\u003c\/p\u003e \u003cp\u003e9.2 Radicals based exclusively on sulfur and nitrogen 319\u003c\/p\u003e \u003cp\u003e9.2.1 NS • and SNS • 319\u003c\/p\u003e \u003cp\u003e9.2.2 S3 N3 • 320\u003c\/p\u003e \u003cp\u003e9.2.3 S3 N2 •+ and related radical cations 320\u003c\/p\u003e \u003cp\u003e9.2.4 Poly(thiazyl), (SN)X 322\u003c\/p\u003e \u003cp\u003e9.3 “Organothiazyl” radicals 323\u003c\/p\u003e \u003cp\u003e9.3.1 Thioaminyl radicals 323\u003c\/p\u003e \u003cp\u003e9.3.2 1,2,3,5-Dithiadiazolyl radicals 329\u003c\/p\u003e \u003cp\u003e9.3.3 1,3,2,4-Dithiadiazolyl radicals 336\u003c\/p\u003e \u003cp\u003e9.3.4 1,3,2-Dithiazolyl radicals 339\u003c\/p\u003e \u003cp\u003e9.3.5 1,2,3-Dithiazolyl radicals 342\u003c\/p\u003e \u003cp\u003e9.3.6 Bis(1,2,3-dithiazole) and related radicals 345\u003c\/p\u003e \u003cp\u003e9.3.7 1,2,4-Thiadiazinyl radicals 348\u003c\/p\u003e \u003cp\u003e9.3.8 1,2,4,6-Thiatriazinyl and -selenatriazinyl radicals 349\u003c\/p\u003e \u003cp\u003e9.3.9 Larger cyclic thiazyl radicals 355\u003c\/p\u003e \u003cp\u003e9.4 Thiazyl radicals as “advanced materials” 355\u003c\/p\u003e \u003cp\u003e9.4.1 Charge transport properties of thiazyl radicals 356\u003c\/p\u003e \u003cp\u003e9.4.2 Thiazyl radical-based charge transfer salts 360\u003c\/p\u003e \u003cp\u003e9.4.3 Magnetic properties of thiazyl radicals 364\u003c\/p\u003e \u003cp\u003e9.5 Conclusions 373\u003c\/p\u003e \u003cp\u003eReferences 373\u003c\/p\u003e \u003cp\u003e\u003cb\u003e10. Stable Radicals of the Heavy p-Block Elements 381\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eJari Konu and Tristram Chivers\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e10.1 Introduction 381\u003c\/p\u003e \u003cp\u003e10.2 Group 13 element radicals 382\u003c\/p\u003e \u003cp\u003e10.2.1 Boron 382\u003c\/p\u003e \u003cp\u003e10.2.2 Aluminum, gallium, and indium 384\u003c\/p\u003e \u003cp\u003e10.3 Group 14 element radicals 388\u003c\/p\u003e \u003cp\u003e10.3.1 Cyclic group 14 radicals 389\u003c\/p\u003e \u003cp\u003e10.3.2 Acyclic group 14 radicals 391\u003c\/p\u003e \u003cp\u003e10.4 Group 15 element radicals 395\u003c\/p\u003e \u003cp\u003e10.4.1 Phosphorus 395\u003c\/p\u003e \u003cp\u003e10.4.2 Arsenic, antimony, and bismuth 400\u003c\/p\u003e \u003cp\u003e10.5 Group 16 element radicals 400\u003c\/p\u003e \u003cp\u003e10.5.1 Sulfur 400\u003c\/p\u003e \u003cp\u003e10.5.2 Selenium and tellurium 401\u003c\/p\u003e \u003cp\u003e10.6 Group 17 element radicals 402\u003c\/p\u003e \u003cp\u003e10.7 Summary and future prospects 403\u003c\/p\u003e \u003cp\u003eReferences 404\u003c\/p\u003e \u003cp\u003e\u003cb\u003e11. Application of Stable Radicals as Mediators in Living-Radical Polymerization 407\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eAndrea R. Szkurhan, Julie Lukkarila and Michael K. Georges\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e11.1 Introduction 407\u003c\/p\u003e \u003cp\u003e11.2 Living polymerizations 408\u003c\/p\u003e \u003cp\u003e11.2.1 Living-radical polymerization background 408\u003c\/p\u003e \u003cp\u003e11.3 Stable free radical polymerization 409\u003c\/p\u003e \u003cp\u003e11.3.1 Background of the work performed at the Xerox Research Centre of Canada 409\u003c\/p\u003e \u003cp\u003e11.3.2 General considerations and mechanism 410\u003c\/p\u003e \u003cp\u003e11.3.3 Unimolecular initiators 411\u003c\/p\u003e \u003cp\u003e11.3.4 Persistent radical effect 413\u003c\/p\u003e \u003cp\u003e11.3.5 Requirements of stable radicals as mediating agents 413\u003c\/p\u003e \u003cp\u003e11.3.6 Nitroxides as mediating agents 414\u003c\/p\u003e \u003cp\u003e11.3.7 Nitroxides and their ability to moderate polymerizations 414\u003c\/p\u003e \u003cp\u003e11.3.8 Rate enhancement of stable free radical polymerization through the use of additives 416\u003c\/p\u003e \u003cp\u003e11.4 Non-nitroxide-based radicals as mediating agents 416\u003c\/p\u003e \u003cp\u003e11.4.1 Triazolinyl radicals 416\u003c\/p\u003e \u003cp\u003e11.4.2 Verdazyl radicals 417\u003c\/p\u003e \u003cp\u003e11.4.3 Other radicals as mediators 418\u003c\/p\u003e \u003cp\u003e11.5 Aqueous stable free radical polymerization processes 420\u003c\/p\u003e \u003cp\u003e11.5.1 Living-radical miniemulsion polymerization 421\u003c\/p\u003e \u003cp\u003e11.5.2 Emulsion polymerization 422\u003c\/p\u003e \u003cp\u003e11.5.3 Other aqueous polymerization processes 423\u003c\/p\u003e \u003cp\u003e11.6 The application of stable free radical polymerization to new materials 423\u003c\/p\u003e \u003cp\u003e11.6.1 Statistical copolymers 423\u003c\/p\u003e \u003cp\u003e11.6.2 Block copolymers 424\u003c\/p\u003e \u003cp\u003e11.7 Conclusions 425\u003c\/p\u003e \u003cp\u003eList of abbreviations 425\u003c\/p\u003e \u003cp\u003eReferences 425\u003c\/p\u003e \u003cp\u003e\u003cb\u003e12. Nitroxide-Catalyzed Alcohol Oxidations in Organic Synthesis 433\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eChristian Brückner\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e12.1 Introduction 433\u003c\/p\u003e \u003cp\u003e12.2 Mechanism of TEMPO-catalyzed alcohol oxidations 434\u003c\/p\u003e \u003cp\u003e12.3 Nitroxides used as catalysts 435\u003c\/p\u003e \u003cp\u003e12.3.1 Monomeric nitroxides 435\u003c\/p\u003e \u003cp\u003e12.3.2 Ionic liquid nitroxides 436\u003c\/p\u003e \u003cp\u003e12.3.3 Supported nitroxides 436\u003c\/p\u003e \u003cp\u003e12.4 Chemoselectivity: oxidation of primary vs secondary alcohols 437\u003c\/p\u003e \u003cp\u003e12.5 Chemoselectivity: oxidation of primary vs benzylic alcohols 438\u003c\/p\u003e \u003cp\u003e12.6 Oxidation of secondary alcohols to ketones 439\u003c\/p\u003e \u003cp\u003e12.7 Oxidations of alcohols to carboxylic acids 439\u003c\/p\u003e \u003cp\u003e12.7.1 Oxidations leading to linear carboxylic acids 439\u003c\/p\u003e \u003cp\u003e12.7.2 (Diol) oxidations leading to lactones 443\u003c\/p\u003e \u003cp\u003e12.8 Stereoselective nitroxide-catalyzed oxidations 444\u003c\/p\u003e \u003cp\u003e12.9 Secondary oxidants used in nitroxide-catalyzed reactions 446\u003c\/p\u003e \u003cp\u003e12.9.1 Elemental halogens 446\u003c\/p\u003e \u003cp\u003e12.9.2 Sodium hypochlorite (bleach) 446\u003c\/p\u003e \u003cp\u003e12.9.3 Bis(acetoxy)iodobenzene (BAIB) 447\u003c\/p\u003e \u003cp\u003e12.9.4 Oxygen (air) 448\u003c\/p\u003e \u003cp\u003e12.9.5 Peroxides 449\u003c\/p\u003e \u003cp\u003e12.9.6 Other organic secondary oxidants 450\u003c\/p\u003e \u003cp\u003e12.9.7 Anodic, electrochemical oxidation 451\u003c\/p\u003e \u003cp\u003e12.10 Use of nitroxide-catalyzed oxidations in tandem reactions 451\u003c\/p\u003e \u003cp\u003e12.11 Predictable side reactions 453\u003c\/p\u003e \u003cp\u003e12.11.1 Oxidations of sulfur 453\u003c\/p\u003e \u003cp\u003e12.11.2 Oxidations of nitrogen 453\u003c\/p\u003e \u003cp\u003e12.11.3 Oxidations of carbon 454\u003c\/p\u003e \u003cp\u003e12.12 Comparison with other oxidation methods 454\u003c\/p\u003e \u003cp\u003e12.13 Nitroxide-catalyzed oxidations and green chemistry 455\u003c\/p\u003e \u003cp\u003eAcknowledgements 456\u003c\/p\u003e \u003cp\u003eReferences 456\u003c\/p\u003e \u003cp\u003e\u003cb\u003e13. Metal–Nitroxide Complexes: Synthesis and Magnetostructural Correlations 461\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eVictor Ovcharenko\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e13.1 Introduction 461\u003c\/p\u003e \u003cp\u003e13.2 Two types of nitroxide for direct coordination of the metal to the nitroxyl group 462\u003c\/p\u003e \u003cp\u003e13.2.1 Complexes containing only \u0026gt;N−•O as a coordinating group 462\u003c\/p\u003e \u003cp\u003e13.2.2 Complexes containing \u0026gt;N−•O and other functional groups as donor fragments 464\u003c\/p\u003e \u003cp\u003e13.3 Ferro- and ferrimagnets based on metal–nitroxide complexes 465\u003c\/p\u003e \u003cp\u003e13.3.1 Molecular magnets based on 1-D systems 470\u003c\/p\u003e \u003cp\u003e13.3.2 Molecular magnets based on 2-D systems 474\u003c\/p\u003e \u003cp\u003e13.3.3 Molecular magnets based on 3-D systems 480\u003c\/p\u003e \u003cp\u003e13.4 Heterospin systems based on polynuclear compounds of metals with nitroxides 483\u003c\/p\u003e \u003cp\u003e13.4.1 Reactions whose products retain both the multinuclear fragment and nitroxide 484\u003c\/p\u003e \u003cp\u003e13.4.2 Transformation of polynuclear fragments in reactions with nitroxides 487\u003c\/p\u003e \u003cp\u003e13.4.3 Transformation of both the polynuclear fragment and the starting nitroxide 489\u003c\/p\u003e \u003cp\u003e13.5 Breathing crystals 490\u003c\/p\u003e \u003cp\u003e13.6 Other studies of metal–nitroxides 494\u003c\/p\u003e \u003cp\u003e13.6.1 Analytical applications 494\u003c\/p\u003e \u003cp\u003e13.6.2 NMR spectroscopy 494\u003c\/p\u003e \u003cp\u003e13.6.3 Stabilization of nitroxides with β-hydrogen atoms 496\u003c\/p\u003e \u003cp\u003e13.6.4 Increased reactivity 496\u003c\/p\u003e \u003cp\u003e13.6.5 Hidden exchange interactions 497\u003c\/p\u003e \u003cp\u003e13.6.6 Contrast agents 499\u003c\/p\u003e \u003cp\u003e13.7 Conclusions 500\u003c\/p\u003e \u003cp\u003eReferences 500\u003c\/p\u003e \u003cp\u003e\u003cb\u003e14. Rechargeable Batteries Using Robust but Redox Active Organic Radicals 507\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eTakeo Suga and Hiroyuki Nishide\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e14.1 Introduction 507\u003c\/p\u003e \u003cp\u003e14.2 Redox reaction of organic radicals 508\u003c\/p\u003e \u003cp\u003e14.3 Mechanism and performance of an organic radical battery 509\u003c\/p\u003e \u003cp\u003e14.4 Molecular design and synthesis of redox active radical polymers 512\u003c\/p\u003e \u003cp\u003e14.4.1 Poly(methacrylate)s and poly(acrylate)s 512\u003c\/p\u003e \u003cp\u003e14.4.2 Poly(vinyl ether)s and poly(allene)s 514\u003c\/p\u003e \u003cp\u003e14.4.3 Poly(cyclic ether)s 514\u003c\/p\u003e \u003cp\u003e14.4.4 Poly(norbornene)s 514\u003c\/p\u003e \u003cp\u003e14.4.5 Poly(acetylene)s 514\u003c\/p\u003e \u003cp\u003e14.4.6 Poly(styrene)s 515\u003c\/p\u003e \u003cp\u003e14.4.7 Combination of radicals with biopolymers and ionic liquids 515\u003c\/p\u003e \u003cp\u003e14.5 A totally organic-based radical battery 515\u003c\/p\u003e \u003cp\u003e14.6 Conclusions 517\u003c\/p\u003e \u003cp\u003eReferences 518\u003c\/p\u003e \u003cp\u003e\u003cb\u003e15. Spin Labeling: A Modern Perspective 521\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eLawrence J. Berliner\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e15.1 Introduction 521\u003c\/p\u003e \u003cp\u003e15.2 The early years 522\u003c\/p\u003e \u003cp\u003e15.3 Advantages of nitroxides 523\u003c\/p\u003e \u003cp\u003e15.4 Applications of spin labeling to biochemical and biological systems 524\u003c\/p\u003e \u003cp\u003e15.4.1 Stoichiometry and specificity: proteins and enzymes 524\u003c\/p\u003e \u003cp\u003e15.4.2 The reporter group approach: who makes the news? 525\u003c\/p\u003e \u003cp\u003e15.5 Distance measurements 526\u003c\/p\u003e \u003cp\u003e15.5.1 Metal–spin label distance measurements 526\u003c\/p\u003e \u003cp\u003e15.5.2 Spin label–spin label distance measurements 526\u003c\/p\u003e \u003cp\u003e15.5.3 Example of strong dipolar interactions 527\u003c\/p\u003e \u003cp\u003e15.5.4 Multiple-quantum EPR and distance measurements 528\u003c\/p\u003e \u003cp\u003e15.6 Site directed spin labeling (SDSL): how is it done? 529\u003c\/p\u003e \u003cp\u003e15.6.1 The SDSL paradigm 530\u003c\/p\u003e \u003cp\u003e15.6.2 SDSL parameters 530\u003c\/p\u003e \u003cp\u003e15.7 Other spin labeling applications 531\u003c\/p\u003e \u003cp\u003e15.7.1 pH sensitive spin labels 532\u003c\/p\u003e \u003cp\u003e15.7.2 Spin labeled DNA – structure, dynamics and sequence analysis 532\u003c\/p\u003e \u003cp\u003e15.8 Conclusions 534\u003c\/p\u003e \u003cp\u003eReferences 534\u003c\/p\u003e \u003cp\u003e\u003cb\u003e16. Functional in vivo EPR Spectroscopy and Imaging Using Nitroxide and Trityl Radicals 537\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eValery V. Khramtsov and Jay L. Zweier\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e16.1 Introduction 537\u003c\/p\u003e \u003cp\u003e16.2 Nitroxyl radicals 538\u003c\/p\u003e \u003cp\u003e16.3 Triarylmethyl (trityl) radicals 539\u003c\/p\u003e \u003cp\u003e16.4 In vivo EPR oximetry using nitroxyl and trityl probes 539\u003c\/p\u003e \u003cp\u003e16.4.1 Magnetic resonance approaches for in vivo oximetry 540\u003c\/p\u003e \u003cp\u003e16.4.2 Nitroxide probes for EPR oximetry 540\u003c\/p\u003e \u003cp\u003e16.4.3 TAM oximetric probes 545\u003c\/p\u003e \u003cp\u003e16.5 EPR spectroscopy and imaging of pH using nitroxyl and trityl probes 547\u003c\/p\u003e \u003cp\u003e16.5.1 pH-sensitive nitroxyl radicals 547\u003c\/p\u003e \u003cp\u003e16.5.2 Dual function pH- and oxygen-sensitive trityl radicals 553\u003c\/p\u003e \u003cp\u003e16.6 Redox- and thiol-sensitive nitroxide probes 556\u003c\/p\u003e \u003cp\u003e16.6.1 Nitroxides as redox-sensitive EPR probes 556\u003c\/p\u003e \u003cp\u003e16.6.2 Disulfide nitroxide biradicals as GSH-sensitive EPR probes 558\u003c\/p\u003e \u003cp\u003e16.7 Conclusions 562\u003c\/p\u003e \u003cp\u003eAcknowledgements 563\u003c\/p\u003e \u003cp\u003eReferences 563\u003c\/p\u003e \u003cp\u003e\u003cb\u003e17. Biologically Relevant Chemistry of Nitroxides 567\u003cbr\u003e\u003c\/b\u003e\u003ci\u003eSara Goldstein and Amram Samuni\u003c\/i\u003e\u003c\/p\u003e \u003cp\u003e17.1 Introduction 567\u003c\/p\u003e \u003cp\u003e17.2 Mechanisms of nitroxide reactions with biologically relevant small radicals 569\u003c\/p\u003e \u003cp\u003e17.3 Nitroxides as SOD mimics 571\u003c\/p\u003e \u003cp\u003e17.4 Nitroxides as catalytic antioxidants in biological systems 573\u003c\/p\u003e \u003cp\u003e17.5 Conclusions 576\u003c\/p\u003e \u003cp\u003eAcknowledgements 576\u003c\/p\u003e \u003cp\u003eReferences 576\u003c\/p\u003e \u003cp\u003eIndex 579\u003c\/p\u003e\u003c\/font\u003e\u003c\/p\u003e\r\n\r\n\u003cp\u003e\u003cfont size=\"3\"\u003eSubject Areas: Chemistry [\u003ca title=\"See our other books on Chemistry\" href=\"https:\/\/freshlyprintedbooks.co.uk\/search?q=%22Chemistry%20%5BPN%5D%22\"\u003ePN\u003c\/a\u003e]\u003c\/font\u003e\u003c\/p\u003e\r\n\r\n\r\n\u003c\/font\u003e","brand":"Wiley","offers":[{"title":"Brand New","offer_id":52278028075288,"sku":"9780470770832","price":138.99,"currency_code":"GBP","in_stock":true}],"thumbnail_url":"\/\/cdn.shopify.com\/s\/files\/1\/0730\/2037\/5320\/files\/9780470770832.jpg?v=1781456426","url":"https:\/\/freshlyprintedbooks.co.uk\/products\/stable-radicals-fundamentals-and-applied-aspects-of-odd-electron-compounds-hardback-9780470770832","provider":"Freshly Printed Books","version":"1.0","type":"link"}